Materials for finishing textiles and processes for producing and using the same



United States PatentOfitice 2,693,460 Patented Nov. 2, 1954 MATERIALS FUR PROCESSES Eon PRODUCING AND'USING The present invention-relates to materialstand-prdo ess'es for imparting improvedv properties to textile: mate-- rials, and to textile materialstreated therewith. More particularly, the presentinvention'relates to'novel resim ous condensation products capable of impartingtthe prop erties of durable water'repellency, shrink resistance and crease resistance to textile materials treated therewith:

In thefinishingof textile materials, such as ray'oni fab'-' rics and of fabrics containingirayon blends which are-"to be utilized, for example, in the manufactureofrainwear and the like, it is desirablethat waterrepellent properties be imparted thereto. Forobvious' reasons, thewater repellency imparted to suchfabric's sho'ulwbe very high initially in'order torender the fabrics-suitable -for the pur poses for whichthey are 1 to be -used: Also, it is desirable that the water repellency"of'suchfabrics be durable; that is, that the treated fabrics retain their water repellent characteristics after being-"subjected tothe ordinary laun dering and dry cleaning operations normally employed m the cleansing of such fabrics. In'additi'on; any treatmerit of textile materials to render the same" water repellent should be suchtha'tthe hand" orfeel of the treated fabric is not objectionably altered thereby; that is, there should be no excessive "weighting ofthe fabric-inor should the fabric take on any harshnessof feel.

It is also often common-practice to" treat the same fabrics with one or more agents't'o render-thefabr'ic'stable against shrinkage and resista'nt toward: CI'CBLSlHgQBDdQ-Vfil')" often, to impart a wool-likeh'andor feel t'o the fabric;

Where all of the above properties are desired -in the finished fabric, it wouldnaturally be advantageous to'be able to combine the above treatment-in -suchmanner-j that only one operation is required. To accomplrshfihrs; the material utilized for imparting: water repellericy-tdtextile materials should be compatible in the I same'treat ng bath with the materials normally used-to: impart; shrink resistance and crease resistance to textile m a terials and thus capable of being applied to the fabric-mthe same treating operation. Furthermore, the-water repellent material employed in such operation sho'uldbe of such character as not to impair the curing characteristics of the materials employed for the stabilizationfo'f the fabric'nor' toim'pair the 'efliciency of the said treatmenhnor should itin any-way impair thehandof the'treated goods whlch would normally be obtained as aresultofthe stabiliiation treatment alone.

In accordance with the present invention,=-a1id as one aspect thereof, there are provided materials capable of imparting a high degree of water repellency to'fabrrcs treated therewith, and which display all of theproprtie's and characteristics desired'of' such'ma-terials a'soutlined above. Further, the water'repellency' imparted totextile materials by the use of the-water repellent materials of the present invention is-highly durable,'-being substantial- 1y unaffected after having-beensubjected to several cleaning or laundering operations;

As another aspect-of thepresent invention there areprovided materials which, in addition to imparting durable water repellent properties to textile" materials treated therewith, also impart a high degree of crease resistance and; dimensional stability to the said:textile-materials.-

The materials provided ii -accordance with-the-present invention and'which are suitable: for finishingtextilematerials to impartthe above describedprop'erties to sa'id-textile materials are heat-convertible resinous condensation products; stable'at normal room temperatures, obtaincd by-reaeting anitr'ogenous compound of the group consistin'gfof urea, thiourea, mono-'alkylated'urea, mono-alkylated-thioureas, guanyl urea; biuret, dicyandiamide andguanidine with amaterial, such as paraformaldehyde, which furnishes formaldehyde underthe reaction conditions and with a lower aliphatic alcohol preliminarily under alkaline conditions'and then under acid conditions to forma:resinoustpartial condensation product of the said materials, and thereafter reacting the said partial condensation product under acid-conditions'with a hydrophobic material of the group-consisting of higher amides, higher amines; andhigher alcohols to obtain a heat-convertible: resinous condensationproduct, capable of polymerize tion: or of further condensationunder heating conditions to an insoluble state.

To obtain heat-convertible resinous condensation prod nets with the materials above set'forth, having theprop erties-and-characteristics of those of the present invention, that'i's, products which may be employed in the finishing of-textilematerials and-which are capable, upon suitable further treatment, ofpolymerizing or reacting further u on.the treated fabric toirnpart highly water repellent characteristicsand/ or crease resistant and shrink resistant q'ualitiesthereto, it is essential that the materials utilized I in. thepreparation of the said condensation products be l'y 'mentioned, under the conditions required to secure the formationrof a resinous condensation product, the reaction proceeds 'so rapidl'y that it is impossible to obtain a satisfactory lresinous condensation product capable of use in the finishingof textile materials. Upon such reaction, there is obtained instead a hard, insoluble resinous materiali The reaction of urea, formaldehyde and'a lower aliphatic 'alcohol to'form an'N,N'bis-(alkoxymethyl) uron,

Y corresponding to the'reaction' of one mol urea, 4 mols of' formaldehyde and 2 mols of a'lower aliphatic-alcohol has also been described. This compound is a very stable liquidmaterial which'is unusually resistant to the normal catalytic action of acids' upon urea-formaldehyde condensates and toward heating, and therefore has no tendency to' fornr polymerization products. Therefore, when it is attempted to react this material with the hydrophobiccompounds employed in the preparation of the resinous condeiiastion products of the present inven-' tion, a product is obtainedwhich is'incapable of further condensation to forman insoluble resinous material.

It has beenfound in'accordance with'the present in-' vention that if the materials employed to'provide thecondensation products described herein are employed in the ratios of 1 mol of the nitrogenous compound, 255-3 .5-'mols of'paraformaldehyde or other suitableform aldehyde providing compound, and 3.0-4.0 mols ofalower aliphatic alcohol and reacted under the conditions hereinafter setforth to format partial condensationprod uct thereof, and 'the product thus obtained is then reacted with from-O:1-2;6 mols of a-hydrophobiccomp'ound ofthe type previously described under acid conditionsofreaction, a heat-convertible resinous condensation product isobtained which is capable of utilization in the treat ment of textile materials to impartdurable water-repellent characteristics and/0r crease-resistant and shrink-resistant properties-thereto. It is, of couse, understoodthat-were and the subsequent reaction of the condensation product so obtained with the hydrophobic compound is only carried out till substantially all of the said hydrophobic compound has reacted with the said partial condensation product. The end product thus obtained is a stable heatconvertible resinous product which is soluble in the common organic solvents such as, for example, the alcohols such as ethyl alcohol and butyl alcohol, the common ester solvents such as ethyl acetate and isopropyl acetate, benzene, varsol and carbon tetrachloride, and which is also soluble or easily dispersible in water.

Those compounds prepared according to the present invention wherein the hydrophobic compound is utilized in an amount of from 0.5-2.6 mols per mol of the initial nitrogenous compound employed in the preparation of the resinous partial condensation product formed by the reaction of the nitrogenous compound, formaldehyde and the lower aliphatic alcohol is characterized by its ability to impart a high degree of water-repellency to textile materials which is also extremely durable. Those compounds prepared in accordance with the present invention wherein the hydrophobic compound is employed in the mol ratio of 0.1-0.5 mols per mol of the nitrogenous compound employed in the preparation of the said partial condensation product as described above are likewise water-repellent but are also characterized by their ability to impart a high degree of durable crease-resistance and shrink-resistance to fabrics treated therewith. The latter compounds therefore have definite advantages over those resinous materials in common use in the industry to impart shrink-resistant and crease-resistant characteristics to textile materials but which display little or no waterrepellent properties.

As stated hereinbefore, the nitrogenous compounds which may be utilized in the reactions herein set forth whereby the resinous condensation products of the present invention are prepared, include urea, thiourea, the mono-alkylated ureas, the mono-alkylated thioureas, guanyl urea, biuret, dicyandiamide and guanidine. The mono-alkylated ureas and thioureas are preferably those containing lower alkyl radicals as, for example, N methyl urea, N ethyl urea, N methyl thiourea and N ethyl thiourea. The di-substituted ureas, that is, both the N,N and the N,N di-substituted ureas have not been found to be operative in the preparation of the desired products.

The material utilized to liberate formaldehyde in the reactions described in the present invention should be one wherein the formaldehyde provided is in a substantially anhydrous condition. Thus any of the polymeric forms of formaldehyde may be employed, such as trioxane or paraformaldehyde. Gaseous formaldehyde may also be employed, it merely being required that the materials em ployed be used in such amounts as to provide the mol ratio of formaldehyde required.

Any of the lower aliphatic alcohols may be employed in the preparation of the condensation products of the present invention. Thus methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol or butyl alcohol may all be utilized with the materials described in the preparation of the said condensation products.

The so-called hydrophobic compounds which are reacted with the partial condensation products to provide the heat-convertible condensation products of the present invention are, as has been stated hereinbefore, the higher amides, the higher amines, and the higher alcohols. By the term higher as used in connection with these materials is meant an amide, or an amine, or an alcohol containing a hydrocarbon radical of at least 12 carbon atoms. In the practice of the present invention, those compounds which apparently provide the best results and which are preferred in preparing the products of the present invention are those which contain at least 16 carbon atoms in the hydrocarbon radical. However, those compounds having at least 12 carbon atoms in the hydrocarbon radical have been found to provide satisfactory results when employed in accordance with the present invention. As specific examples of such com pounds there may be mentioned lauramide, myristic acid amide, palmitic acid amide, stearamide, behenic acid amide, montanic acid amide, and in general amides of fatty acids as obtained from naturally occurring fats; laurylamine, hexadecylamine, octadecylamine; and, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol. There may also be employed the amides, amines and alcohols of the higher hydrocarbon materials obtained from the OX0 Process and the Fischer- Tropsch Synthesis, as well as amides, amines and alcohols of synthetic hydrocarbons of at least 12 carbon atoms wherein the hydrocarbon radical consists of an alkyl-aryl chain. Amides, amines and alcohols of rosm or rosin derivatives may also be utilized in preparing the products of the present invention.

In carrying out the present invention, a lower aliphatic alcohol and, for example, paraformaldehyde are charged to a vessel equipped for refluxing the charged materials, together with a sufiicient amount of an alkaline material, such as an alkali metal hydroxide, to render the mixture alkaline; a pH of 8 to 9 being completely satisfactory for the purposes of the present invention. The mixture is then heated until the paraformaldehyde has dissolved, a temperature not in excess of 100 C. usually being sufficient for this purpose. A nitrogenous compound of the class previously described is then added to the solution and heating is continued at a temperature of approximately 7085 C. for approximately 15-20 minutes after the said nitrogenous compound has gone into solution. The pH of the reaction mixture is then reduced to a point within the range of approximately 2.5 to 5.0 and heating is continued at a temperature of -100 C. for approximately 15-20 minutes. At this point a hydrophobic compound, as previously described, is slowly added to the reaction mixture and when addition of the same is completed and the said compound has completely dissolved, the reaction mixture is heated for approximately one hour at a temperature of approximately -l00 C., or until substantially complete reaction of the hydrophobic compound with the remaining components of the reaction mixture has been secured. The product thus obtained is a heat-convertible resinous condensation product stable at normal room temperatures and capable of utilization in the finishing of textile materials to impart water-repellent characteristics and/ or crease-resistant and shrink-resistant properties thereto.

The products obtained as above described, if not already water-soluble or self-emulsifiable, may be emulsified with water by the addition of small quantities of emulsifying agents, thus providing a convenient means for application of the products to textile materials.

In such treatment of textile materials, a treating bath is prepared which satisfactorily may contain from approximately 2%l5% by weight of a resinous condensation product prepared in accordance with the present invention. To such bath there is usually added a latent polymerization catalyst such as ammonium chloride or other suitable acid catalyst such as ammonium sulfate or diammonium phosphate. The textile material to be treated is then immersed in the treating bath as by normal padding operations, the amount of wet pick-up by the fabric being regulated by passing the fabric through squeeze rolls. The impregnated fabric is then dried and cured at temperatures of the order of approximately -180 C.; for example, heating at C. for approximately 6 minutes having been found satisfactory. Depending upon the particular condensation product employed, the fabric thus treated has excellent water-repellent and/or crease-resistant and shrink-resistant characteristics which are retained even upon subsequent laundering and dry cleaning operations.

Depending upon the products of the present invention which are utilized and depending upon the qualities desired in the finished product, there may also be used, together with the products of the present invention, those resins which are in common use in the textile industry for finishing textile materials such as, for example, the methylolurea condensates, or the partially polymerized urea-formaldehyde, melamine-formaldehyde and phenolformaldehyde condensates. Thus, enhanced characteristics of water-repellency, shrink-resistance and crease re sistance may be imparted to textile materials in one operation by means of a single bath treatment.

The following Examples 1 to 10 demonstrate that aspect of the present invention involving the production of resinous condensation products which are capable of imparting a high degree of water repellency to fabrics treated therewith. All amounts given therein are set forth in parts by weight.

Example-1 96-pa'rt's' of methanol, 84' parts of paraformaldehyde' and 0.1 part of caustic soda are charged to a vessel equipped with stirrenthermometer'an'd reflux condenser. Themixture is heated to reflux conditions and-held at such temperature until the paraformaldehyde has dissolved. 60 parts of urea are-added thereto and heating is continued at a temperature of 73 76 C. for approximately 15 minutes. The pH of the reaction mixture is then lowered to approximately 3.0 to 3.5 with phosphoric a'cicl'and heating is continued'for approximately 15 more minutes at a temperature of 75-83 C; 290'parts of stea'ramide are then slowly added to the reactionmixture and after solution of the stearamide therein has been e'tfected, the reaction mixture is'heated for approximately one ho'urat atem'perature of '8386 C. At the endo'f this period there is secured as a condensation product a resinous material capable of imparting water-repellent characteristics to textile materials. The entire reaction as carried out above and inthe succeeding examples is carried-outunder agitation conditions.

A concentrated emulsion, suitable'for use in a textile treating'bath, may be prepared'by adding to the' reaction product obtained above parts of coconut fatty acid and 30 parts of triethanolamine followed by 427 parts of water at 75 C. The mixture is subjected to agitation without heating and, as the temperature begins to fall, a creamy, light colored emulsion forms. Stirring is continued for approximately minutes at a temperature of approximately 6065 C. and theemulsionis'allowedto cool to room temperature withoutstirring. The product thus obtained is readily dispersible in cold or hot water to provide dilute emulsions suitable for application to textile materials.

Example 2 The reaction described in Example 1 isdupIicated except that in place of urea there are substituted 74 parts of N-methyl urea. A product similar'in its characteristics to that obtained in Example 1 is secured.-

Example 3 138parts of ethyl alcohol, 99 parts of paraformaldehyde and 0.2 part of caustic soda are charged to a suitable reaction vessel as described in Example 1 and the materials are refluxed under agitation conditions until solution of the paraformaldehyde has been obtained. 76 parts of thiourea are added and when solution of the same" is secured, the reaction mixture; is heated for approximately 15 minutes at 7075 C. ThepH of the mixture is then lowered to approximately 3.0-3.5 with phosphoric acid and heating is continued for approximately 15 more'minutes. A total of 237.3 parts of be henic acid amide are then slowly added to the reaction mixtureand when addition of the same has been completed, the mixture'is heated for approximately one hour at a temperature of approximately 80-85 C. The product thus obtained is a resinous condensation'product capable of use in accordance with the present invention to impart highly water-repellent characteristics to" textile materials.

Example 4 The reaction described'in Example 3'is duplicated except that in place of thiourea there aresubstituted 104 parts of N-cthyl thiourea. A resinous condensation product having highly durable water-repellent properties is sec'ured.

' Example 5 96'partsof methanol, 84 parts of formaldehyde and 0.1 part of caustic soda are refluxed until the'p'araformaldehyde has dissolved. 84 parts of dicyandiamide are added to the mixture and heating iscontinued at 70--75 C. for 15 minutes. The reaction mixture is then acidified with phosphoric acid toa pH of approximately 3.0'and heating is continued for 15 more minutes at a temperature of 7580 C. 502 parts of lauramide are then slowly added to the reaction mixture and when addition ofthe lauramide has been completed thereaction mixtureis heated for one hour at atemper'ature of- 8085 C. The product thusse'curedis characterized by its ability to impart highly water-repellent properties to textile materials.

112 parts of methanol; 96.parts;off 'paraformaldehyde, and 0.1 part of caustic soda ar'e-refluxed asdescribedin Examplel until solution of the paraformaldehyde is obtained. 60 parts of urea are then added thereto andfthe admixture heated'for approximately 20'minutes at 70 75 C. The pH of theadmixture is lowered'to approximately 3.0-3.5 with phosphoric acid andheating-is-continued for approximately '15 more minutes at a-temperature of 75 -80 C. 269" parts of octadecylamine are then slowly added to the reaction mixture which is then heated at 8086 C. for about one hour. The reaction product thus obtained'has'excellent' water-repellent properties when applied to textile materials;

Example 7 96 parts of methanol, 75 pa'rts of paraformaldehyde, and 0.1 part of caustic' soda are refluxed'under the'con ditions hereinbefore set forth until solution of the para formaldehyde is secured. 102 par-ts ofguany-lureaare added and the admixture heated for approximately 15 minutes at 75 80 C. The;p I-I ofthe;admixture is then reduced to approximately 3.0-3 .5 with phosphoric acid and heating is continued for 15 more minutes. There are then slowly added 370 parts oflaurylamine and heating is continued forone hour at a temperature of 8085 C. The product secured at-the end of this period is a resinous condensation product having water-repellent properties when applied to textile materials in the manner set forth herein.

Example 8' A mixture of 96-partsof methanolgand 84 parts ofparaformaldehyde are refluxed until: solution of the paraformaldehyde is obtained. 103 parts of biuret are added to the reaction mixture and the pH thereof is adjusted to a pH value of 8 to 9 with caustic soda. The reaction mixture is then' refluxed for 15 minutes at Example 9 180 parts of propyl alcohols, 75 parts of paraformaldehyde, and 0.1 part of caustic soda are heated until solution of the'paraformaldehyde is obtained. 60 parts of urea are added thereto and when solution of the same has been obtained, the reaction mixture is heated for 15 minutes at 80-85 C. The pH of the mixture is then lowered to approximately 3.0 to 3.5 with phosphoric acid and heating is continued for approximately another 15 minutes. 270 parts of stearyl alcohol are then slowly added to the reaction mixture and when addition of the same has been completed, the mixture is heated for approximately one hour at 8086 C. There isthus obtained a resinous condensation product capable of imparting permanent water-repellent propertiesto textile materials.

Exam'PIe'JO A mixtureof 138 parts of ethyl alcohol and parts of paraformaldehyde, are refluxed till solution of the paraformaldehyde is'secured; 59'parts' ofguanidine are added to the solution which is then refluxed for about 15 minutes at 75 80C. The pH of the reaction mix ture is then lowered to approximately 3-'-3.5 and refluxing thereof is continued for 1 5 more minutes; 484 parts of cetyl alcohol are" then added'to the reaction mixture which is then again refluxedfor one hour at a temperature of 8085' C. The" resultant product is a heat convertible resinous condensation product capable of imparting durable water-repellent properties to textile materials. 7

As a demonstration of the effectiveness ofthewaterrepellency imparted to textile materials by th'e'products of the present invention textile treating bathswereprepared containing. the" condensation product of Example 1 in varying concentrations by weight a's hereinafter set forth in the table that follows, each bath also containing 18% by weight of a methylolurea thermosetting resin used for shrinkproofing textiles, 0.5% by weight of ammonium hydroxide, and 1.0% by weight of ammonium chloride. Samples of a viscose gabardine suiting fabric were passed through the baths and the excess pick-up was removed therefrom by passing the fabrics through squeeze rolls. The treated fabrics were dried and then cured for minutes at 155 C. The following results with respect to the water-repellency of the treated fabrics were obtained.

Spray Ratings of the Treated Fabric Otlmcientratpn ttrf Watiargtepbelen tea mg a y After 3 After 3 Weight Initial Dry Rayon Cleanings Washes The fabric resulting from the above treatment not only displayed the excellent water-repellent properties shown in the above table, but also had excellent resistance towards shrinkage. Also, no objectionable effects upon the hand or feel of the treated fabric were obtained as a result of the treatment outlined above.

The resinous condensation products of the present invention which are capable of imparting a high degree of shrink-resistance and crease-resistance to textile materials in addition to water-repellent properties are prepared under the same reaction conditions as those employed in preparing the products of Examples 1 to 10 as demonstrated in the following examples.

Example 11 96 parts of methanol and 84 parts of paraformaldehyde are charged to a suitable vessel containing a stirrer, thermometer and reflux condenser. The mixture is then refluxed until all of the paraformaldehyde has dissolved. 60 parts of urea are then added to the reaction mixture and the pH of the same is adjusted to a pH value of about 8-9 with caustic soda. The reaction mixture is then refluxed at a temperature of 7075 C. for 15 minutes, cooled to approximately 50 C. and then acidified with cure such effect by treatment of the fabrics with resinous condensation products secured by modifying the aforesaid products by reaction with approximately 0.1 to 0.5 mol of an aliphatic polyhydric alcohol. Suitable polyhydric alcohols which may be employed include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, glycerol pentaerythritol, sorbitol and mannitol. The following examples are illustrative of the preparation of such products.

Example 13 A mixture of 96 parts of methanol and 84 parts of paraformaldehyde are refluxed until solution of the paraformaldehyde is obtained. parts of urea are added thereto and the pH of the mixture is adjusted to a pH value of 89 with caustic soda. The mixture is then refluxed for 15 minutes at 75 C., cooled to approximately 50 C., acidified with phosphoric acid to a pH of 3-3.5, and refluxed for 15 more minutes at a temperature of 80 C. There are then added thereto 10.6 parts of diethylene glycol and 96.7 parts of stearamide and the mixture is then refluxed for one hour at -85 C. The product thus secured is a liquid resinous condensation product having the properties of those obtained as described in Examples 11 and 12 but capable of imparting a firmer hand to fabrics treated therewith.

Example 14 The reaction described in Example 13 is duplicated except that in place of the diethyleneglycol there are substituted 9.2 parts of glycerol.

Example 15 The reaction described in Example 13 is duplicated except that in place of diethyleneglycol there are substituted 13.6 parts of pentaerythritol.

The effects produced by the products of the above illustrative examples upon textile materials are shown by the data set forth in the table which follows. Samples of a rayon gabardine fabric were impregnated with the products of Examples 11, 13, 14 and 15, respectively, applied from water emulsions containing 9 percent by weight of the said products and were subsequently cured for 10 minutes at 150 C. It is seen that these products by themselves imparted durable water-repellency, dimensional stability and crease-resistance to the fabric in one operation.

phosphoric acid to a pH of approximately 3-3.5. Refluxing of the reaction mixture is then continued for another 15 minutes. 96.7 parts of stearamide are then added to the reaction mixture and after solution of the stearamide is effected, the mixture is heated for one hour at 80-85 C. At the end of this period, a straw colored translucent liquid resinous condensation product is obtained which is capable of imparting a high degree of crease-resistance and shrink-resistance to fabrics treated therewith.

Example 12 112 parts of methanol, 96 parts of paraformaldehyde, and 0.1 part of caustic soda are heated until solution of the paraformaldehyde is obtained. 76 parts of thiourea are then added thereto and when solution of the same has been obtained, the reaction mixture is refluxed at a temperature of 70-75 C. for 15 minutes. 66 parts of octadecylamine are then slowly added to the reaction mixture and when addition of the same has been completed, the mixture is refluxed for approximately one hour at 80-85 C. The product obtained is similar in its properties and characteristics to that of Example 11.

Where it is desired that the treated fabrics have a firmer hand than that obtainable with products of the type illustrated in the foregoing examples, it is possible to se- The above tests for water-repellency, crease-resistance and shrink-resistance were made following the standard procedures set up for such determinations by the American Association of Textile Chemists and Colorists as described in its yearbook for the year 1951.

While the above products and processes of making and using the same constitute preferred embodiments of the present invention, changes may be made therein without departing from the scope of the invention as defined in the appended claims.

What is claimed is:

1. A heat-convertible resinous condensation product suitable for finishing textile materials consisting of the product secured by reacting one mol of a material of the group consisting of urea, thiourea, mono-alkylated ureas, mono-alkylated thiourea, guanyl urea, biuret, dicyandiamide and guanidine with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof, and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of an essence itt ain.tit tes a iphatic.ami contai in at ast .2m;- zbontatomst 2- .A..h a zoon ert .blos e iuous cond nsa on p o uc suitable for finishing textile materials consistingsof the produ -scoured y :roa iuaon mo i-u e with 25 to 32 mo o t a s bstan ial y a hydrou m t ria wh ;ztu n .s t s f rma de y e unde th eac io o d tio and'with 3 vto 4 mols of ,an unsubstituted aliphatic alcohol containing up to 4.,carbon atoms preliminarily und. alk in o ti n and u eq e t y un e oidcon- .dit o secu re inou pa ti c ndens t on P od ther o a d r a e W3. i ssai esi u p rtia ond n tion nt du -unde oeid cond ti n with app natelyt 0.1 to 2.6 mols of steararnide.

3. ,A heat-convertible resinous condensation product suitabl o fin hin te t le mate i l c mprisin the product secured by reacting one;mo l of thiourea'with 2.5 t ..3.-. nol f ma erie hiohfu nish o malde y .under the reaction conditions and:wit h 3 to .4 mols of an unsubstituted aliphatic alcohol containing upto 4 carbo atom pr iinina y uud lka neo nd n vand subsequently under acidconditions tosecure a resinous partial condensation product thereof, ,andthereafter re-- acting said resinous fpartial condensation product under acid conditions with;approximately-,().1 to 2.6 mols of st a a ide.

A A vheatrconvertible resinous condensation product suitabl fi hi g text e materials o p isin the product secured byreactingone mol of urea with 2.5 o 3.5vmol o a m er a h ch furnis esor a dehy .ll l erthereaction-conditions and with 3 :to 4mols of un ubst u d aliph t al oho ontainin up o 4 e o c om p limfinarilyon e alk lin dit n n subsequently under acid conditions to secure a ,resinous partial condensation-product thereof, and thereafter reacting said resinous partial condensation product under acidconditions with approximately.0. l to 2.6 r nols of octadccylamine.

5. A heat-convertible ,resinous condensation product suitable ;for finishing textile materials comprising the product secured by reacting one mol of thiourea with 2.5 to 3.5 molsof ainaterialwhich furnishesformaldehydeunder thereactionconditions and with 3 to 4 mols .Qfan unsubstituted aliphaticalcohol-containing up to 4 carbon atoms preliminarily ;under alkaline conditions :andsubsequently under, aci cond t on to eou e a r i ous partial condensation product thereof and thereafter e 'tina ai sin s pa ti l c nd n ati n pr duc under vacidc ndit s with appr x m tely 3 to 2.6 mo o octadecylamine. i

-6.,A process for preparing a heat-convertible resinous condensation product suitable for finishing textile materials-which consists in reacting one mol of a maite a of t e g p c n i in of rea, thi e mo o- .alhylated ureas, mono alkylatedthioureas, guanyl urea, ,biuret, dicyandiamide,.andguanidine with2 5 to 3.5 mols o'f a substantially anhydrous materialwhich furnishes ,ffor naldehyde under the reaction conditions and with 3 to .4 mols of an unsubstituted aliphatic alcohol contain- .ing up to .4 carbon atoms preliminarily under alkaline conditions and subsequently under I acid conditions to secure a resinous partial condensation productthereof, and thereafter reacting said resinous partial condensation product .under acid conditions with-approximately 0.1 to ,2.6 n iols.of an unsubstitutedaliphatic amide contain- ;ingat least 12carbon atoms.

7. A process for ;preparing a heat-convertible resinous condensation product 'suitable for finishing textile ;materials which consistsin reacting.one-.mol.;of urea with 25 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under {the reaction conditions andwith 3 to4 imolsofan unsubstituted; aliphatic alcohol containing up to 4 carbon atoms preliminarily .under alkaline conditions andsubsequently under acid conditions tosecure a resinous partial condensation product thereof, and thereafter reacting said resinous partial condensationiproduct under acidiconditions with. --approximately 0.1 to 2,6, mols of stearamide.

' '8. A process for;preparing a heat'convertible resinous condensation product suitable for finishing ,textile .materials which consists -,in reacting .one mol of .thiourea with 2:5 to 3:5 .mols of .a substantially, anhydrous ma terial which furnishes formaldehyde -under,, the reaction conditions and with '3 ,to 4 mols ,of an unsubstitu ed aliphatic alcohol containing up to..4 carbon. atomspre- :lirnioati u d alka ne conditions and qsu segueutly 10 under acid conditions-to secure a resinouspartial condensation product thereof, and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6mols of stearamide.

9. A process for preparing a heat-convertible resinous condensation product suitable for finishing textile materials which consists in reacting one mol of urea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof, and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of octadecylannne.

10. A process for preparing a heat-convertible resinous condensation product suitable for finishing textile materials which consists in reacting one mol of thiourea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under me reaction conditions and with 3 to 4 mols ofan unsubstituted aliphatic alcohol containing up to 4 ,carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof, and thereafter reacting said resinous partial condensationproduct under acid conditions with approximately 0.1 to 2.6 mols of octadecylamine.

11. A textile material having improved propertiesof durable water repellency, shrink resistance and crease resistance comprising the product resulting from the impregnation of a textile material with a heat-convertible resinous condensation product secured by reacting one mol of a material of the group consisting of urea, thiourea, mono-alkylated ureas, mono-alkylated thioureas, guanyl urea, biuret, dicyandiamide and guanidine with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atomspreliminarily under alkaline conditions and subsequently underacid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial con densation product under acid conditions with approximately 0.1 to 2.6 mols of a material of the group consisting of unsubstituted aliphatic amides containing at least 12 carbon atoms, unsubstituted aliphatic amines containing at least 12 carbon atoms, and unsubstituted aliphatic alcohols containing at least '12 carbon atoms, and thereafter subjecting said impregnated material to elevated temperatures to insolubilize the said resinous condensation product.

12. A textile material having improved properties of durable water-repellency, shrink-resistance and creaseresistance comprising theproduct resulting from the impregnation of a textile material with a heat convertible resinous condensation product secured by reacting one mol of urea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensationproduct under acid conditions with approximately 0.1 to 2.6 mols of stealamide, and thereafter subjecting said impregnated material to elevated temperatures .to insolubilize the said resinous condensation product.

13. A textile material having improved properties of durable water-repellency, shrink-resistance and crease-resistance comprising the productresulting fromthe impregnation of a textile material with a heat-convertible resinous condensation product secured by reacting one mol of thiourea with 2.5 to 3.5 mols of a material which furnishes formaldehyde underthe reaction conditions and with 3 to 4 molsof an unsubstituted aliphatic alcohol containing up .to 4carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of stearamide, and thereafter subiecting said impregnated material to elevated temperatures to insolubilize the saidresinous ,condensationproduct.

14. A textile material having improved properties of durable water-repellency, shrink-resistance and creaseresistance comprising the product resulting from the mpregnation of a textile material with a heat-convertible resinous condensation product secured by reacting one mol of urea with 2.5 to 3.5 mols of a material WhlCh furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditious to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of octadecylamine, and there after subjecting said impregnated material to elevated temperatures to insolubilize the said resinous condensation product.

15. A textile material having improved properties of durable water-repellency, shrink-resistance and crease-resistance comprising the product resulting from the impregnation of a textile material with a heat-convertible resinous condensation product secured by reacting one mol of thiourea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of octadecylamine, and thereafter subjecting. said impregnated material to elevated temperatures to insolubilize the said resinous condensation product.

16. A textile material having improved properties of durable water-repellency, shrink-resistance and crease-resistance comprising the product resulting from the impregnation of a textile material with a heat-convertible resinous condensation product secured by reacting one mol of urea with 2.5 to 3.5 mols of a material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of stearyl alcohol, and thereafter subjecting said impregnated material to elevated temperatures to insolubilize the said resinous condensation product.

17. A process of finishing textile materials which comprises the steps of impregnating a textile material with a heat-convertible resinous condensation product secured by reacting one mol of a material of the group consisting of urea, thiourea, mono-alkylated ureas, mono-alkylated thioureas, guanyl urea, biuret, dicyandiamide and guanidine with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of a material of the group consisting of unsubstituted aliphatic amides containing at least 12 carbon atoms, unsubstituted aliphatic amines containing at least 12 carbon atoms, and unsubstituted aliphatic alcohols containing at least 12 carbon atoms, and thereafter SllbJBCtlIlg said impregnated textile material to elevated temperatures to insolubilize the said resinous condensation product.

18. process of finishing textile materials which comprises the steps of impregnating a textile material w1th a heat-convertible resinous condensation product secured by reacting one mol of urea with 2.5 to 3.5 mols of a substantally anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol contalnmg up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of stearamide, and thereafter subjecting said impregnated textile material to elevated temperatures to insolubilize the said reslnous condensation product.

19. A process of finishing textile materials which comprises the steps of impregnating a textile material with a heat-convertible resinous condensation product secured by reacting one mol of thiourea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of stearamide, and thereafter subjecting said impregnated textile material to elevated temperatures to insolubilize the said resinous condensation product.

20. A process of finishing textile materials which comprises the steps of impregnating a textile material with a heat-convertible resinous condensation product secured by reacting one mol of urea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of octadecylamine, and thereafter subjecting said impregnated textile material to elevated temperatures to insolubilize the said resinous condensation product.

21. A process of finishing textile materials which comprises the steps of impregnating a textile material with a heat-convertible resinous condensation product secured by reacting one mol of thiourea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of octadecylamine, and thereafter subjecting said impregnated textile material to elevated temperatures to insolubilize the said resinous condensation product.

22. A process of finishing textile materials which comprises the steps of impregnating a textile material with a heat-convertible resinous condensation product secured by reacting one mol of urea with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of stearyl alcohol, and thereafter subjecting said impregnated textile material to elevated temperatures to insolubilize the said resinous condensation product.

2 A heat convertible resinous condensation product suitable for finishing textile materials consisting of the product secured by reacting one mol of a material of the group consisting of urea, thiourea, mono-alkylated ureas, mono-alkylated thiourea, guanyl urea, biuret, dicyandiamide and guanidine with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde uuder the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbonatoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof, and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of an unsubstituted aliphatic amine containing at least 12 carbon atoms.

24. A process for preparing a heat convertible resi wlls condensation product suitable for finishing textile materials which consists in reacting one mol of a material of the group consisting of urea, thiourea, monoalkylated ureas, mono-alkylated thioureas, guanyl urea, biuret, dicyandiamide, and guanidine with 2.5 to 3.5 mols of a substantially anhydrous material which furnishes formaldehyde under the reaction conditions and with 3 to 4 mols of an unsubstituted aliphatic alcohol containing up to 4 carbon atoms preliminarily under alkaline conditions and subsequently under acid conditions to secure a resinous partial condensation product thereof, and thereafter reacting said resinous partial condensation product under acid conditions with approximately 0.1 to 2.6 mols of an unsubstituted aliphatic amine containing at least 12 carbon atoms.

References Cited in the file of this patent Number 5 2,108,113 2,217,372 2,254,001 2,286,752 2,374,648 10 2,486,459

Number UNITED STATES PATENTS Name Date Eisenmann Feb. 15, 1938 Ludwig Oct. 18, 1940 Conaway Aug. 26, 1941 Mighton June 16, 1942 Burke May 1, 1945 Bock Nov. 1, 1947 FOREIGN PATENTS Country Date Great Britain Nov. 3, 1947 

1. A HEAT-CONVERTIBLE RESINOUS CONDENSATION PRODUCT SUITABLE FOR FINISHING TEXTILE MATERIAL CONSISTING OF THE PRODUCT SECURED BY REACTING ONE MOL OF A MATERIAL OF THE GROUP CONSISTING OF UREA, THIOUREA, MONO-ALKYLATED UREAS, MONO-ALKYLATED THIOUREA, GUANYL UREA, BIURET, DICYANDIAMIDE AND GUANIDINE WITH 2.5 TO 3.5 MOLS OF A SUBSTANTIALLY ANHYDROUS MATERIAL WHICH FURNISHES FORMALDEHYDE UNDER THE REACTION CONDITIONS AND WITH 3 TO 4 MOLS OF AN UNSUBSTITUTED ALIPHATIC ALCOHOL CONTAINING UP TO 4 CARBON ATOMS PRELIMINARILY UNDER ALKALINE CONDITIONS AND SUBSEQUENTLY UNDER ACID CONDITIONS TO SECURE A RESINOUS PARTIAL CONDENSATION PRODUCT THEREOF, AND THEREAFTER REACTING SAID RESINOUS PARTIAL CONDENSATION PRODUCT UNDER ACID CONDITIONS WITH APPROXIMATELY 0.1 TO 2.6 MOLS OF AN UNSUBSTTITUTED ALIPHATIC AMIDE CONTAINING AT LEAST 12 CARBON ATOMS. 